Freeze-thaw stable paint formulation

ABSTRACT

The present invention relates to a pre-paint composite comprising an aqueous slurry of TiO 2  particles and a polymeric binder, wherein from 35 to 90 weight percent of the polymeric binder is attached to the TiO 2  particles, based on the weight of polymeric binder in the pre-paint composite. The pre-composite of the present invention is useful in paint compositions, particularly those that require freeze-thaw stability

BACKGROUND OF THE INVENTION

The present invention relates to a paint formulation with improvedfreeze-thaw stability. Binder composites comprising TiO₂ particlesencapsulated with polymer, as described for example in U.S. Pat. No.8,283,404 and WO 2012/116025, have been shown to improve hiding in paintformulations, sometimes dramatically so. Unfortunately, paintsformulated with these composites often exhibit poor freeze-thawstability. It would therefore be an advance in the art of paintformulations to provide a formulation with excellent hiding coupled withfreeze-thaw stability.

SUMMARY OF THE INVENTION

The present invention addresses a need by providing, in one aspect, aprocess for preparing a pre-paint composite comprising the steps of: a)contacting together a mixture of: i) an aqueous dispersion of TiO₂particles and an adsorbing sulfur acid functionalized polymer; ii) ananionic surfactant; iii) sodium styrene sulfonate; and iv) a redoxinitiator system; to form a first composite intermediate; then b)contacting under emulsion polymerization conditions the first compositeintermediate with a first monomer emulsion comprising: i) methylmethacrylate or styrene or a combination thereof; ii) a C₁-C₁₀ alkylacrylate; and iii) a carboxylic acid containing monomer under emulsionpolymerization conditions; to form a second composite intermediate; thenc) contacting the second composite intermediate with a second monomeremulsion comprising: i) styrene or methyl methacrylate or a combinationthereof; ii) a C₁-C₁₀ alkyl acrylate; iii) a carboxylic acid containingmonomer; and iv) a secondary alcohol ethoxylate of the formulaC₁₀₋₁₅H₂₂₋₃₂O(CH₂CH₂O)_(x)H; to form an aqueous dispersion of TiO₂particles with incomplete attachment of polymeric binder; where x isfrom 15 to 50 and the O(CH₂CH₂O)_(x)H group is bonded to a CH group onthe C₁₀₋₁₅H₂₂₋₃₂ chain.

In a second, the present invention is a pre-paint composite comprisingan aqueous slurry of TiO₂ particles and attached and unattachedpolymeric binder, and a sufficient amount of a secondary alcoholethoxylate of the formula C₁₀₋₁₅H₂₂₋₃₂O(CH₂CH₂O)_(x)H to give 35 to 90weight percent attachment of polymeric binder to the TiO₂ particles,based on the weight of total polymeric binder in the pre-paintcomposite, where x is from 15 to 50; and the O(CH₂CH₂O)_(x)H group isbonded to a CH group on the C₁₀₋₁₅H₂₂₋₃₂ chain.

The present invention addresses a need in the art by providing apre-paint composite that is useful in paint compositions that requirefreeze-thaw stability.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the present invention is a process for preparing apre-paint composite comprising the steps of: a) contacting together amixture of: i) an aqueous dispersion of TiO₂ particles and an adsorbingsulfur acid functionalized polymer; ii) an anionic surfactant; iii)sodium styrene sulfonate; and iv) a redox initiator system; to form afirst composite intermediate; then b) contacting under emulsionpolymerization conditions the first composite intermediate with a firstmonomer emulsion comprising: i) methyl methacrylate or styrene or acombination thereof; ii) a C₁-C₁₀ alkyl acrylate; and iii) a carboxylicacid containing monomer under emulsion polymerization conditions; toform a second composite intermediate; then c) contacting the secondcomposite intermediate with a second monomer emulsion comprising: i)styrene or methyl methacrylate or a combination thereof; ii) a C₁-C₁₀alkyl acrylate; iii) a carboxylic acid containing monomer; and iv) asecondary alcohol ethoxylate of the formula C₁₀₋₁₅H₂₂₋₃₂O(CH₂CH₂O)_(x)H;to form an aqueous dispersion of TiO₂ particles with incompleteattachment of polymeric binder; where x is from 15 to 50 and theO(CH₂CH₂O)_(x)H group is attached to a CH group on the C₁₀₋₁₅H₂₂₋₃₂chain.

As used herein, the term “adsorbing sulfur acid functionalized polymer”refers to a polymeric TiO₂-adsorbing dispersant that contains sulfuracid functionality, preferably arising from sulfur-acid functionalmonomers such as sulfoethyl methacrylate, sulfopropyl methacrylate,styrene sulfonic acid, vinyl sulfonic acid, and 2-acrylamido-2-methylpropanesulfonic acid, and salts thereof, with 2-acrylamido-2-methylpropanesulfonic acid and sulfoethyl methacrylate being preferred.

The sulfur acid functionalized polymer is preferably an adsorbingamphoteric polymer, more preferably a polymer that is prepared from thecopolymerization of an ethylenically unsaturated sulfur-acid functionalmonomer and an ethylenically unsaturated amine functional monomer.Examples of suitable ethylenically unsaturated amine functional monomersinclude dimethylaminoethyl methacrylate, dimethylaminopropylmethacrylamide, and t-butylaminoethyl methacrylate, withdimethylaminoethyl methacrylate (DMAEMA) being preferred.

In addition to containing amine and sulfur acid functionality, theamphoteric polymer may additionally include functional groups arisingfrom the copolymerization of water-soluble monomers such as hydroxyethylmethacrylate, methacrylamide, acrylamide, or methacrylic acid, oracrylic acid, or combinations thereof.

The dispersion of TiO₂ and the preferred adsorbing amphoteric polymerare advantageously prepared by slowly adding, with concomitant grinding,the TiO₂ to an aqueous solution of the amphoteric polymer. The preferredsolids content of the TiO₂/amphoteric polymer dispersion is in the rangeof 70 to 80 weight percent based on the weight of TiO₂, amphotericpolymer, and water.

In a preferred first step, the TiO₂/amphoteric polymer dispersion isadded to a vessel followed by addition of a) an anionic surfactant suchas those well known in the art, preferably as an aqueous solution; andb) preferably an aqueous solution of sodium styrene sulfonate, morepreferably as a 5 to 20 weight percent solution based on the weight ofwater and sodium styrene sulfonate.

The redox initiator system is then advantageously contacted with themixture to initiate polymerization to form a first compositeintermediate. As used herein, the term “redox initiator system” refersto a combination of a reducing agent, an oxidizing agent, and a metalion catalyst. Examples of suitable oxidizing agents include persulfatessuch as ammonium and alkali metal persulfates; hydroperoxides, such ast-butyl hydroperoxide and cumene hydroperoxide; peroxides such asbenzoyl peroxide, caprylyl peroxide, and di-t-butyl peroxide; peresterssuch as t-butyl peracetate, t-butyl perphthalate, and t-butylperbenzoate; percarbonates; and perphosphates; with t-butylhydroperoxide being preferred.

Examples of suitable reducing agents include ascorbic acid, isoascorbicacid, malic acid, glycolic acid, oxalic acid, lactic acid, andthioglycolic acid; an alkali metal hydrosulfite such as sodiumhydrosulfite; a hyposulfite such as potassium hyposulfite; or ametabisulfite such as potassium metabisulfite; and sodium formaldehydesulfoxylate.

Suitable accelerators include halide and sulfate salts of cobalt, iron,nickel, and copper, used in small amounts. An example of a preferredredox initiator system is t-butyl hydroperoxide/isoascorbic acid/Fe⁺².Preferably, the accelerator is added prior to the addition of theoxidizing and reducing agents. It is further preferred that theoxidizing and reducing agents are added over time to maintain arelatively even level of radical flux over the course of the addition ofmonomers.

The first monomer emulsion is preferably added to the first compositeintermediate after a waiting period of from 30 seconds to about 10minutes, more preferably from 1 minute to 5 minutes. It is understoodthat the term “a first monomer emulsion” is used to refer to an aqueousemulsion of one or more monomers, preferably of more than one monomer. Apreferred combination of monomers in the first monomer emulsioncomprises methyl methacrylate; a carboxylic acid monomer such as acrylicacid, methacrylic acid, or itaconic acid, preferably in the range of 0.3to 3 weight percent, based on the weight of total monomers; and a C₂-C₁₀acrylate monomer such as butyl acrylate, ethyl acrylate, or ethylhexylacrylate or a combination thereof.

The first monomer emulsion may also include a crosslinking monomer,which, at low levels, has been found to improve the hiding efficiency ofthe encapsulated particles. The crosslinking monomer is preferably amultiethylenically unsaturated crosslinking monomer, more preferably adiethylenically unsaturated monomer, used at a level sufficient to forma polymer that is resistant to deformation, preferably in the range offrom 0.05 to 3 weight percent based on the weight of the first monomers.Examples of suitable crosslinking monomers include allyl methacrylate,ethylene glycol dimethacrylate, butylene glycol dimethacrylate, anddivinyl benzene at a concentration of from 0.1 to 2 weight percent,based on the weight of total first monomers.

The first monomers are polymerized under polymerization conditions,preferably at a starting temperature of from 20° C. to 75° C. to form afirst stage polymer having the desired T_(g).

A second stage polymerization is then carried out by adding a secondmonomer emulsion to the vessel containing the second compositeintermediate. The second monomer emulsion comprises styrene or methylmethacrylate or a combination thereof; ii) a C₁-C₁₀ alkyl acrylate,preferably ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or acombination thereof; iii) a carboxylic acid containing monomer,preferably methacrylic acid, acrylic acid, or itaconic acid, morepreferably methacrylic acid; and iv) a secondary alcohol ethoxylatesurfactant of the formula C₁₀₋₁₅H₂₂₋₃₂O(CH₂CH₂O)_(x)H, preferablyC₁₂₋₁₄H₂₆₋₃₀O(CH₂CH₂O)_(x)H, where x is preferably 15 to 50, preferably20 to 40. Commercially available examples of suitable surfactantsinclude TERGITOL™ 15-S-40 Secondary Alcohol Ethoxylate Surfactant andTERGITOL™ 15-S-20 Secondary Alcohol Ethoxylate Surfactant (A Trademarkof The Dow Chemical Company or its Affiliates). The concentration of thesecondary alcohol ethoxylate surfactant in the second monomer emulsionis preferably from 0.1 weight percent, more preferably from 0.2 weightpercent, and most preferably from 0.3 weight percent, to preferably 3.0weight percent, more preferably to 2.5 weight percent, more preferablyto 1.5 weight percent, and most preferably to 1 weight percent, based onthe total weight of the pre-paint composite. The second monomer emulsionpreferably further comprises a salt of a sulfur acid monomer, morepreferably sodium styrene sulfonate.

A second stage polymerization is then carried out to form an aqueousdispersion of TiO₂ particles with incomplete attachment of polymericbinder (the pre-paint composite). The second stage polymer preferablyhas a T_(g) of from −40 ° C. to 40 ° C., as calculated by the Foxequation.

The weight-to-weight ratio of total monomers to TiO₂ solids ispreferably from 0.8 to 1.6, more preferably from 1.0 to 1.4.

In a second aspect, the present invention is a pre-paint compositecomprising an aqueous slurry of TiO₂ particles and attached andunattached polymeric binder, and a sufficient amount of a secondaryalcohol ethoxylate of the formula C₁₀₋₁₅H₂₂₋₃₂O(CH₂CH₂O)_(x)H to give 35to 90 weight percent attachment of polymeric binder to the TiO₂particles, based on the weight of total polymeric binder in thepre-paint composite, where x is from 15 to 50; and the O(CH₂CH₂O)_(x)Hgroup is attached to a CH group on the C₁₀₋₁₅H₂₂₋₃₂ chain. Preferably,the pre-paint composite comprises from 0.2 to 2.5 weight percent of asecondary alcohol ethoxylate represented by the formulaC₁₂₋₁₄H₂₆₋₃₀O(CH₂CH₂O)_(x)H, where x is from 20 to 40. More preferably,the extent of polymeric binder attachment to TiO₂ particles ranges from50, and most preferably from 60 weight percent attached binder, to 90,more preferably to 85 weight percent attached binder.

The pre-paint composite of the present invention can be used to preparea coatings formulation, which comprises the pre-paint composite and oneor more components selected from the group consisting of dispersants,defoamers, surfactants, solvents, additional binders, thickeners,extenders, coalescents, biocides, and colorants. It has beensurprisingly discovered that the addition of the secondary alcoholethoxylate surfactant to the second monomer emulsion results in a markedimprovement in the freeze-thaw properties of the final paintformulation. It has further been discovered that addition of thesecondary alcohol ethoxylate surfactant in the final paint formulationbut not in the second monomer emulsion does not result in a formulationwith improved freeze-thaw properties. It appears that incompleteattachment of polymeric binder to TiO₂ particles, as manifested bygreater than 10 weight percent polymeric binder in the water phase,correlates with good freeze-thaw stability.

In the following examples, TiO₂ amphoteric polymer slurry was preparedsubstantially as described in US2010/0298483, Examples 2 and 5.

Example 1A Preparation of Pre-Paint Composite with Secondary AlcoholEthoxylate

Monomer Emulsion 1 (ME1) was prepared by mixing water (45 g), PolystepA-16-22 surfactant (9 g), butyl acrylate (123.3), methacrylic acid (2.16g), and methyl methacrylate (78.8 g).

Monomer Emulsion 2 (ME2) was prepared by mixing water (225 g), PolystepA-16-22 surfactant (60.3 g), styrene (398.7 g), methacrylic acid (9.9g), butyl acrylate (612.9 g), sodium styrene sulfonate (5.2 g), andTERGITOL™ 15-S-40 Secondary Alcohol Ethoxylate Surfactant (70% aqueoussolution, 36 g).

TiO₂ amphoteric polymer slurry (1420.7 g) and water (265.5 g) were addedto a 4-neck 5-L round bottom flask equipped with a stirrer, athermocouple, a nitrogen inlet, and a reflux condenser was added. Themixture was heated to 30° C. under N₂, whereupon Polystep A-16-22surfactant (10.8 g), an aqueous solution of sodium styrene sulfonate(8.6 g in 50 g water), an aqueous solution of t-butyl hydroperoxide(1.71 g in 22 g water), a solution of isoascorbic acid (0.95 g in 22 gwater), and a mixture of 0.15% aqueous iron sulfate septa hydratesolution (42.8 g) and 1% aqueous ethylene diamine tetraacetic acid(EDTA, 1.1 g) were sequentially added to the flask. Co-feed catalyst(17.1 g t-butyl hydroperoxide in 212 g water) and co-feed activator (9.5g isoascorbic acid in 212 g water) were fed to the flask at a rate of1.6 g/min Three minutes later, ME1 was fed to the reactor at a rate of12.9 g/min and the flask temperature rose to 50° C. After ME1 additionwas complete, the monomer emulsion vessel was rinsed with deionizedwater (27 g) into the flask. The co-feed catalyst and activator additionwere continued for 3 min and turned off, and the flask was held at 50°C. The co-feed catalyst and activator addition were resumed 18 min laterat a rate of 1.6 g/min ME2 was fed to the reactor 2 min later, at a rateof 13.5 g/min and the reactor temperature was controlled at 68° C. AfterME2 addition was complete, the monomer emulsion vessel was rinsed withdeionized water (27 g) into the flask, and the co-feed solutionadditions were continued for 20 min until addition was complete. Theflask was cooled to room temperature; when the temperature of the flaskreached 45° C., a solution of ACRYSOL™ ASE-60 Anionic Thickener(Trademark of The Dow Chemical Company or Its Affiliates, 19.4 g in 40 gwater) was added over 30 min, followed by the addition of a solution of29% aqueous ammonium hydroxide (14.4 g) and water (36 g). When thecontents reached room temperature, they were filtered to remove any gel.The filtered dispersion was found to have a solids content of 57.42%with a pH of 8.6 and 38 ppm of dry gel.

Comparative Example 1A Preparation of Pre-Paint Composite without aSecondary Alcohol Ethoxylate

The procedure of Example 1A was substantially followed except that ME2did not contain TERGITOL™ 15-S-40 Secondary Alcohol EthoxylateSurfactant.

Example 2A Preparation of Pre-Paint Composite with a Secondary AlcoholEthoxylate

The procedure of Example 1A was substantially followed except that halfas much TERGITOL™ 15-S-40 Secondary Alcohol Ethoxylate Surfactant (70%aqueous solution, 18 g) was used in the ME2 formulation.

Example 3A Preparation of Pre-Paint Composite with a Secondary AlcoholEthoxylate

The procedure of Example 1A was substantially followed except that twiceas much TERGITOL™ 15-S-40 Secondary Alcohol Ethoxylate Surfactant (70%aqueous solution, 72 g) was used in the ME2 formulation.

Example 4A Preparation of Pre-Paint Composite with a Secondary AlcoholEthoxylate

The procedure of Example 1A was substantially followed except thatTERGITOL™ 15-S-20 Secondary Alcohol Ethoxylate Surfactant (70% aqueoussolution, 36 g) was used in the ME2 formulation.

Paints were prepared from the various pre-paint composites and KUfreeze-thaw stability and hiding were measured. For each example thetotal pigment volume concentration (PVC) was 40 and volume solids was42% for each paint formulation.

Example 1B Paint Formulation

The formulation for Example 1B is shown in Table 1. TAMOL, TRITON,PRIMAL, ROPAQUE, CARBITOL, and ACRYSOL are all Trademarks of The DowChemical Company or its Affiliates.

TABLE 1 Paint Formulation Using Example 1A Pre-Paint Composite MaterialName % Wt. Water 7.05 Sodium Hexametaphosphate 0.03 Defoamer 0.27TAMOL ™ 945 Dispersant 0.14 TRITON ™ CF-10 Surfactant 0.19 PropyleneGlycol 4.00 HEC Thickener 0.21 Extender 11.662-Amino-2-methyl-1-propanol (95% active in water) 0.15 Grind Total 23.69Example 1A Pre-Paint Composite 63.05 PRIMAL ™ CM-219EF Binder 2.06ROPAQUE ™ Ultra E Opaque Polymer 9.62 Butyl CARBITOL ™ Solvent 1.22Silicone Resin 0.06 ACRYSOL ™ RM-2020 Rheology Modifier 0.30 Paint Total100.00

Examples 2B-4B Paint Formulations

Paints were prepared using Example 2A-4A pre-paint composites usingsubstantially the same formulation as shown in Table 1.

Comparative Example 1B Paint Formulation without Secondary AlcoholEthoxylate

A Paint was formulated in accordance with Table 1 except that thePre-Paint Composite contained no secondary alcohol ethoxylate (as perComparative Example 1A).

Comparative Example 2B Paint Formulation with Secondary AlcoholEthoxylate Added Separately

A paint was formulated in accordance with Table 1 except that thePre-Paint Composite contained no secondary alcohol ethoxylate (as perComparative Example 1A); TERGITOL™ 15-S-40 Secondary Alcohol EthoxylateSurfactant (70% aqueous solution, 0.54 g) was added separately to thePaint in this example.

Test Method for Freeze-Thaw Stability

Paint samples (˜130 g) were placed in plastic containers and KUviscosities measured; the containers were then capped and taped andplaced in a freezer maintained at −10 ° C. for 16 h. After the sampleswere removed from the freezer, they were allowed to thaw at ambienttemperature for 4 h or more to melt all ice crystals. The paints werethen hand-mixed and KU viscosities were measured again (constituting onefreeze-thaw cycle). This procedure was repeated two more times tomeasure viscosity changes in paints after three freeze-thaw cycles.

Test Method for Measuring Polymeric Binder Attached to TiO₂

Composite (˜20 g) was added to DI water (˜12 g) in 50 -mL centrifugationvials, which were capped then vigorously hand mixed for about 1 min Thediluted sample was put in a Fischer Scientific Legend X1R centrifuge setat 7000 rpm (acceleration and deceleration at setting 9) and 20° C. for30 min Approximately 5 mL of the supernatant was removed and solidscontent measured in duplicate after removal of liquid at 150° C. for 20min using weight differences. The weight of the centrifuged solid plugat the bottom was also measured. The quantity of solids in thesupernatant was assumed to be polymer unattached to the TiO₂. Percent ofattached polymeric binder was calculated as:

(Total Polymer−unattached Polymer)/Total Polymer*100.

Kubelka-Munk S/mil Test Method

Four draw-downs were prepared on Black Release Charts (Leneta FormRC-BC) for each paint using a 1.5 -mil Bird draw down bar and the chartsallowed to dry overnight. Using a template, 3.25″×4″ rectangles were cutout with an X-ACTO knife on each chart. The Y-reflectance was measuredusing a X-Rite Color i7 Spectrophotometer in each of the scribed areasfive times measuring on a diagonal starting at the top of the rectangleand the average Y-reflectance recorded. A thick film draw down wasprepared for each paint on the Black Release Charts using a 3″ 25 milblock draw down bar and the charts were allowed to dry overnight. TheY-reflectance was measured in five different areas of the draw down andthe average Y-reflectance recorded. Kubelka-Munk hiding value S is givenby Equation 1:

$\begin{matrix}{S = {\frac{R}{X \times \left( {1 - R^{2}} \right)} \times \ln \frac{1 - \left( {R_{B} \times R} \right)}{1 - \frac{R_{B}}{R}}}} & {{Equation}\mspace{14mu} 1}\end{matrix}$

where X is the average film thickness, R is the average reflectance ofthe thick film and R_(B) is the average reflectance over black of thethin film. X can be calculated from the weight of the paint film(W_(pf)), the density (D) of the dry film; and the film area (A). Filmarea for a 3.25″×4″ template was 13 in².

${X({mils})} = \frac{{W_{pf}(g)} \times 1000\; \left( {{mil}\text{/}{in}} \right)}{{D\left( {{lbs}\text{/}{gal}} \right)} \times 1.964\left( {g\text{/}{in}^{3}\text{/}{lbs}\text{/}{gal}} \right) \times {A({in})}}$

The Freeze-Thaw and Hiding (S/mil) data for Paint Formulations Examples1B-4B and Comparative Examples 1B-2B are summarized in Table 2.

In the Table, SAE refers to Secondary Alcohol Ethoxylate; wt. % ActiveSAE is based on the weight of the pre-paint composite; 15-S-40 and15-S-20 refer to TERGITOL™ 15-S-40 Secondary Alcohol EthoxylateSurfactant and TERGITOL™ 15-S-20 Secondary Alcohol EthoxylateSurfactant, respectively; ME2 refers to the fact that the 15-S-40 or15-S-20 is added to the second monomer emulsion; PAINT refers to thefact that the SAE is 15-S-40 is added to the Paint; % Attachment refersto the percentage of polymeric binder attached to the TiO₂; and F/Trefers to freeze/thaw.

TABLE 2 Freeze-Thaw and Hiding Data for Paint Formulations Example No.C. Ex. 1B C. Ex. 2B Ex. 1B Ex. 2B Ex. 3B Ex. 4B wt. % Active SAE 0 1.240.62 0.62 0.31 0.62 SAE — 15-S-40 15-S-40 15-S-40 15-S-40 15-S-20 SAEAdded to: — ME2 ME2 PAINT ME2 ME2 % Attachment 95 64 76 95 83 76FREEZE-THAW Initial KU 94 98 93 94 89 89 KU after 1^(st) F/T cy. >140100 90 >140 90 91 KU after 2^(nd) F/T cy. — 98 90 — 90 91 KU after3^(rd) F/T cy. — 98 90 — 83 83 RESULT FAIL PASS PASS FAIL PASS PASSHIDING: S/Mil 7.16 6.55 7.05 6.77 6.56 Std. Dev. 0.02 0.04 0.04 0.020.03

The data show acceptable freeze-thaw and hiding profiles when secondaryalcohol ethoxylate with 20 to 40 ethoxylate units was included in thesecond monomer emulsion. ME2 that did not contain this surfactant showedpoor freeze-thaw profiles. The data suggest a correlation betweenacceptable freeze-thaw and hiding properties with incomplete attachmentof polymeric binder to the TiO₂ particles.

1. A pre-paint composite comprising an aqueous dispersion of TiO₂particles and a polymeric binder, wherein from 35 to 90 weight percentof the polymeric binder is attached to the TiO₂ particles, based on theweight of polymeric binder in the pre-paint composite.
 2. The pre-paintcomposite of claim 1 wherein from 60 to 85 weight percent of thepolymeric binder is attached to the TiO₂ particles, based on the weightof polymeric binder in the pre-paint composite.
 3. The pre-paintcomposite of claim 1 which further comprises a secondary alcoholethoxylate of the formula C₁₂₋₁₄H₂₆₋₃₀O(CH₂CH₂O)_(x)H; wherein x is from15 to 50 and the O(CH₂CH₂O)_(x)H group is bonded to a CH group on theC₁₂₋₁₄H₂₆₋₃₀ chain.
 4. The pre-paint composite of claim 2 which furthercomprises a secondary alcohol ethoxylate of the formulaC₁₀₋₁₅H₂₂₋₃₂O(CH₂CH₂O)_(x)H; wherein x is from 15 to 50 and theO(CH₂CH₂O)_(x)H group is bonded to a CH group on the C₁₀₋₁₅H₂₂₋₃₂ chain.5. The pre-paint composite of claim 4 wherein x is from 20 to
 40. 6. Thepre-paint composite of claim 1 wherein the polymer binder is a copolymerof 1) styrene or methyl methacrylate; and 2) a C₁-C₁₀-alkyl acrylate;and 3) a carboxylic acid containing monomer.
 7. The pre-paint compositeof claim 1 which further comprises an adsorbing sulfur acidfunctionalized polymer.
 8. The pre-paint composite of claim 7 whereinthe sulfur acid functionalized polymer is an adsorbing amphotericpolymer.
 9. The pre-paint composite of claim 7 wherein the adsorbingsulfur acid functionalized polymer comprises structural units of2-acrylamido-2-methyl propanesulfonic acid or sulfoethyl methacrylate orsalts thereof or a combination thereof.
 10. The pre-paint composite ofclaim 8 wherein the adsorbing amphoteric polymer comprises structuralunits of dimethylaminoethyl methacrylate and 2-acrylamido-2-methylpropanesulfonic acid.
 11. The pre-paint composite of claim 10 whereinadsorbing amphoteric polymer further comprises structural units of oneor more water-soluble polymers selected from the group consisting ofhydroxyethyl methacrylate, methacrylamide, acrylamide, methacrylic acid,and acrylic acid.
 12. The pre-paint composite of claim 1 wherein thebinder is a styrene-butyl acrylate binder.